TWI422552B - A kind of transparent and heat shielding material and manufacturing method thereof - Google Patents

Description

Transparent heat insulating material and preparation method thereof

The invention relates to a transparent heat insulating material and a preparation method thereof, in particular to a transparent heat insulating film made of the transparent heat insulating material, which has high transparency and excellent infrared ray blocking property.

In order to achieve the purpose of energy saving and carbon reduction, in the prior art, the glass of buildings and automobiles is usually insulated and energy-saving by attaching a layer of heat insulating material. The physical properties of metal oxides have good thermal insulation effects and have been widely used as materials for blocking infrared rays.

For example, U.S. Patent No. 5,385,751 discloses a fluorine-doped tungsten oxide infrared barrier material. However, the method of manufacturing is expensive, and the manufacturing cost is high because of the use of chemical vapor deposition (Chemical Vapor Deposition).

Japanese Laid-Open Patent Publication No. Hei 9-12338 discloses an infrared ray-blocking film comprising a composite tungsten oxide composed of a tungsten element and a specific element such as Group IA of the periodic table, but the method of sputtering is to use a sputtering method. When the transparent glass substrate carrying the infrared ray blocking membrane is exposed to the high temperature plasma, the infrared ray blocking membrane is easily damaged by the high energy ion beam in the plasma during the forming process; and, in order to reduce the defect density of the infrared ray blocking membrane Annealing equipment is required for heat treatment, and has the disadvantages of complicated process and high manufacturing cost.

Japanese Laid-Open Patent Publication No. 2003-121884 discloses a method for preparing a tungsten trioxide powder, the method comprising the steps of: dissolving tungsten hexafluoride in alcohol, separating the precipitate from the solution, and at a temperature of 100 to 500 ° C. The precipitate is heated to obtain a tungsten trioxide powder. Moreover, the use of the tungsten trioxide powder is suitable for use as a barrier infrared material.

US Publication No. 2006/0178254 discloses a process for preparing a composite tungsten oxide, the method steps of which include:

a) selecting one of tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder or ammonium tungstate powder;

b) selecting a monomer containing M element or a compound; the M element includes elements such as H, He, an alkali metal, an alkaline earth metal or a rare earth;

c) mixing the powder of step a) and step b) in a certain ratio, and adding ethanol or water to prepare a tungsten oxide hydrate, and then drying the tungsten oxide hydrate;

d) subjecting the dried tungsten oxide hydrate of step c) to the following two-stage heat treatment:

D-1) performing a first-stage heat treatment at a sintering temperature of 100 to 850 ° C in a reducing gas atmosphere, for example, under a condition of passing hydrogen (H ₂ );

D-2) waiting for temporary recovery to room temperature, and then performing a second-stage heat treatment at a sintering temperature of 650 to 1200 ° C in an inert gas atmosphere, for example, under argon (Ar);

e) The composite tungsten oxide which has completed the two-stage heat treatment is subjected to fine grinding treatment to obtain composite tungsten oxide fine particles of the general formula MxWyOz.

The composite tungsten oxide fine particles obtained by the method of the above publication have sufficient ability to shield infrared rays and are suitable for use as a barrier infrared material. However, in the process of the composite tungsten oxide, since the two-stage heat treatment is required, there are still disadvantages in that the process is complicated in the preparation process.

In order to solve the above problems of the prior art, the main object of the present invention is to provide an adjustable composite metal tungsten oxychloride with high transparency and high heat insulation effect, and a method for preparing the same, which requires only a single step heat treatment in the process, so The process is simple and low-cost, and the composite metal tungsten oxychloride (hereinafter referred to as composite tungsten oxychloride) has both high transparency and high heat insulation effect, and is suitable for use as a barrier infrared material. use.

The composite tungsten oxychloride of the present invention is formed by co-doping at a suitable ratio with a cerium (Cs) element and one or more metal element chlorides containing tin (Sn) or bismuth (Sb) or bismuth (Bi). a composite tungsten oxychloride material having a chemical formula of Cs _x N _y WO _3-Z Cl _C , wherein Cs is 铯; N is tin (Sn) or bismuth (Sb) or bismuth (Bi); W is tungsten; O is oxygen ; X, Y, Z, C are all positive and meet the following conditions: X≦1.0; Y≦1.0; Y/X≦1.0; Z≦0.6 and C≦0.1; and, in the composite tungsten oxychloride material The cesium (Cs) is easy to emit a free electron, with doped tin (Sn) or bismuth (Sb) or bismuth (Bi) metal elements to emit four to five free electrons, each with a different absorption wavelength range, but for both The common wavelength band of the infrared wavelength of 800~2000nm has a particularly strong absorption capacity.

The composite tungsten oxychloride preparation method of the invention comprises the following steps:

a. taking tungsten hexachloride dissolved in ethanol to prepare a solution A;

b. taking an appropriate amount (proportion) of cesium chloride (CsCl) and tin (Sn) or bismuth (Sb) or bismuth (Bi) metal element chloride together with water to prepare a solution B;

c. forming a precipitate by solution co-deposition of solution A and solution B;

d. The composite tungsten oxychloride powder is obtained by subjecting the precipitate of step c to a single sintering heat treatment.

The composite tungsten oxychloride method of the present invention is a single-sintering heat treatment at a sintering temperature of 450 to 800 ° C in an environment in which a certain proportion of hydrogen or/and argon gas is introduced. The purpose of introducing hydrogen or/and argon into the heat treatment is to avoid the reduction of a part of the composite tungsten oxide to tungsten oxide (WO ₃ ) and to weaken the absorption characteristics of the near-infrared rays. Moreover, the hydrogen and argon can be extended at the same time. Weather resistance of tungsten oxychloride.

The composite tungsten oxychloride method of the invention is suitable for a composite tungsten oxychloride material of the chemical formula Cs _x N _y WO _3-Z Cl _C , wherein N is tin (Sn) or bismuth (Sb) or bismuth (Bi) metal The element, under the condition that the co-doping ratio (Y/X) of the N metal element to the Cs element is less than or equal to 1.0 (ie, Y/X≦1.0), as long as the addition amount of the N metal element is adjusted, the N metal element pair The co-doping ratio (Y/X) of the Cs element will change accordingly. Under the appropriate high-temperature furnace heat treatment conditions, the physical properties of the prepared composite tungsten oxychloride material will follow the co-doping ratio (Y/X). The change shows a different infrared blocking rate. When the co-doping ratio (Y/X) of the N metal element to the Cs element is higher, the infrared ray blocking ratio (heat insulating effect) of the obtained composite tungsten oxychloride material is relatively higher. Therefore, the method of the present invention can produce adjustable composite tungsten oxychloride with different thermal insulation levels according to different use requirements in the market.

The composite tungsten oxychloride of the invention contains chlorine element and has an infrared ray rejection of more than 70% (ie >70%), and is suitable for forming a transparent transparent heat-insulating film, which can be attached to the glass of buildings and automobiles to achieve heat insulation. Energy-saving effects can also be applied to composite substrates for electronic components.

The composite tungsten oxychloride method of the invention has the following characteristics:

1. Only one sintering heat treatment is required in the preparation method, the process is simple and the cost is saved;

2. The composite tungsten oxide prepared according to the method has excellent infrared blocking rate and visible light transmittance;

3. The composite tungsten oxide prepared according to the method has long-term quality stability and can be used in industry.

The composite tungsten oxychloride of the present invention utilizes cerium (Cs) element and tin (Sn) or bismuth (Sb) or bismuth (Bi) metal element chloride, and is co-doped at a proper ratio to form a composite tungsten oxychloride. The material has a better infrared band barrier property, and has a superior absorption capacity for light of a specific wavelength of 800 to 2000 nm, especially an infrared wavelength of 800 to 1000 nm, and its physical properties also have better visible light penetration. The rate is suitable for high transparency and high heat insulation materials that block infrared rays.

Further, the composite tungsten oxychloride of the present invention, as a result of the life test, has long-term quality stability as shown in Fig. 1, and is available for industrial use.

The composite tungsten oxychloride of the present invention has a chemical formula of Cs _x N _y WO _3-Z Cl _C , wherein Cs is 铯; N is tin (Sn) or bismuth (Sb) or bismuth (Bi); W is tungsten; Oxygen; X, Y, Z, C are all positive and meet the following conditions:

X≦1.0;

Y≦1.0;

Y/X≦1.0;

Z≦0.6 and C≦0.1;

When the N element coexists with the cerium (Cs) element and the co-doping ratio (Y/X) of the N element to the cerium (Cs) element is less than or equal to 1.0, ie, Y/X ≦ 1.0, the composite tungsten oxychloride of the present invention The compound has a high transparency and a high heat insulation multiplication effect; when the codoping ratio (Y/X) is more than 1.0, the transparency and heat insulation effect of the composite tungsten oxychloride are poor.

The composite tungsten oxychloride of the invention contains chlorine element and is made by co-doping of strontium (Cs) element interstitial with tin (Sn) or antimony (Sb) or bismuth (Bi) metal elements, and the transparent heat insulation effect thereof The composite metal tungsten oxyhalide, which is obviously superior to other common elements or a combination thereof, is suitable for forming a highly transparent heat-insulating film, which can be applied to the glass of buildings and automobiles to achieve the effect of heat insulation and energy saving. For example, the composite tungsten oxychloride of the present invention has a better heat insulating effect than a composite tungsten oxyhalide using a halogen group F, Br, I or At element.

As shown in FIG. 2, the composite tungsten oxychloride process of the present invention comprises the following steps:

a. taking tungsten hexachloride dissolved in ethanol to prepare a solution A;

b. taking an appropriate amount (ratio) of cerium chloride (CsCl) and a metal element-containing chloride together with water to prepare a solution B; wherein the metal element is selected from tin (Sn) or bismuth (Sb) or bismuth ( Bi) one or more of the groups formed;

c. The solution A and the solution B are co-deposited to form a precipitate comprising at least tungsten oxychloride (WOCl ₄ ) and chloride; wherein the composition of the chloride precipitate depends on the composition of the solution B, Including a cerium chloride precipitate, one or more of tin chloride, cerium chloride or cerium chloride;

d. subjecting the precipitate of step c to a single sintering heat treatment to obtain a sintered powder;

The solvent removal step and the drying step may be previously performed on the precipitate of the step c before the heat treatment.

When the solvent removal step is carried out, the precipitate of the step c is subjected to a solvent removal treatment by a centrifugation method or a filtration method.

When the drying step is carried out, the precipitate of the filtered solvent is placed in an environment at a temperature of 115 to 145 ° C, and dried by heating for 1 hour.

When performing a single sintering step, the precipitate of the step c or the dried precipitate is placed in a tubular furnace or a square furnace (hereinafter referred to as a high temperature furnace) for high-temperature sintering, and the sintering condition is at a heating rate of 2 to 10 ° C / min. At the same time, hydrogen (H ₂ ) and an inert gas such as argon (Ar) are introduced. Under the condition of hydrogen (H ₂ ) as reducing gas, the sintering temperature of the high temperature furnace is raised from room temperature to 450~800 °C, and the heat treatment is continued for 1~2 hours; after cooling down, the chemical formula is Cs. _x N _y WO _3-Z Cl _C composite tungsten oxychloride sintered powder (hereinafter, simply referred to as composite tungsten oxychloride powder); when performing a single sintering heat treatment, the heating rate of the high temperature furnace is controlled to be per minute 2~10 ° C, and maintaining the fixed temperature for the composite tungsten oxychloride for a predetermined time of sintering heat treatment, for the composite tungsten oxychloride has achieved the purpose of drying and annealing. The composite tungsten oxychloride powder subjected to the above heat treatment has a chemical composition stability, and the variability is reduced, and a composite tungsten oxychloride which does not form an inappropriate element ratio is obtained, and has a good near-infrared region absorption property.

The composite tungsten oxychloride powder of the present invention is a raw material for forming a highly transparent heat insulating film, and the steps further include:

e. finely grinding the prepared composite tungsten oxychloride powder;

f. taking an appropriate amount of the composite tungsten oxychloride fine powder of step e, adding a binder and a specific formulation auxiliary, and then stirring and grinding to form a slurry (or coating liquid);

The purpose of adding the auxiliary agent is to help the prepared composite tungsten oxide fine powder to achieve uniform dispersion. The auxiliary agent to be used includes one or more of a coupling agent, a surfactant, a dispersing agent, a high molecular polymer modifier or a UV absorber.

g. Applying the coating liquid of the step f to the transparent substrate polyethylene terephthalate film (PET film) by wet coating to form a transparent heat insulating film.

For example, the composite tungsten oxychloride fine powder of the step e is added to a toluene solvent to prepare a solution of a composite tungsten oxychloride fine powder of 20% by weight (weight ratio), and 6 wt% of a polymer type dispersant is added and utilized. 1 mm cerium zirconium beads were ground and dispersed to obtain a dispersion of composite tungsten oxychloride having a particle diameter of less than 80 nm.

The dispersion liquid was mixed with an acrylic resin (commercial model SSM7, manufactured by Nanya Plastics Co., Ltd.) to prepare a coating liquid having a dispersion of 20% by weight (by weight). The coating liquid is applied to the transparent substrate by wet coating, and the transparent substrate may be glass, polyethylene terephthalate film (PET) or polyethylene naphthalate (PEN). , polycarbonate (PC), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), acrylic resin (Acrylic Resin), aromatic polyester (PAr), aromatic polyester A polymer film such as CycloOlefin Polymer (COP) was dried at 120 ° C for 2 minutes to obtain a transparent heat-insulating film.

The transparent heat-insulating film obtained according to the above steps has excellent infrared high barrier properties and high visible light transmittance. Hereinafter, the present invention will be further described in detail by way of examples.

The evaluation of the physical properties of the transparent heat-insulating film of the present invention is based on the following test methods.

1. Visible light transmittance (VLT%) test: A light transmittance tester (Haze Meter) of the model TC-HIII manufactured by Japanese Denkyoku Denshoku Co., Ltd., tested in accordance with JIS K7705 test standard, transparent test Light transmittance and haze value of the heat insulating film.

The higher the visible light transmittance, the better the transparency of the transparent heat-insulating film.

2. Infrared (IR cut%) barrier rate test: The model of the LT-3000 infrared barrier rate tester manufactured by Nissan HOYA was used to test the infrared blocking rate of the polyester film according to the JIS R3106 test standard.

The test result is that the higher the infrared blocking rate, the better the heat insulation effect of the polyester film.

3. The total index of transparency and heat insulation (ie, VLT%+IR cut%) is the sum of the above two measured data. The higher the value, the better the transparency and heat insulation effect.

Example 1

A mixture of tungsten hexachloride and ethanol is used to prepare a blue solution A having a pH of about 0; another cesium chloride (CsCl) and ruthenium trichloride (SbCl ₃ ) are combined with water at a ratio of 1 mole to 0.1 mole. The transparent solution B was prepared by mixing. The two solutions A and B were precipitated by a co-deposition method. Its chemical reaction formula is as follows:

2WCl ₆ +C ₂ H ₅ OH+3H ₂ O → WOCl ₄ ( ↓ )+WO ₂ Cl ₂ ( ↓ )+6HCl+C ₂ H ₅ OH ; WOCl ₄ ( ↓ )+WO ₂ Cl ₂ ( ↓ )+C ₂ H ₅ OH+CsCl+SbCl ₃ +3H ₂ O → 2WO ₃ ( ↓ )+Cs ⁺ +Sb ^{+ 3} +Cl ^- +6HCl+C ₂ H ₅ OH

Next, the obtained precipitate is placed in a high-temperature furnace, and a certain flow of argon gas and hydrogen gas are introduced, and the high-temperature furnace is raised from room temperature to 485 under the condition that the heating rate of the high-temperature furnace is 2 ° C per minute. 515 ° C (expressed at an average temperature of 500 ° C), and heat treatment was continued for 1 hour.

After the heat treatment is completed, a composite tungsten oxide containing cerium and lanthanum elements having a pH of about 7 is obtained, and the reaction formula is as follows:

2WOCl ₄ +2WO ₂ Cl ₂ +2Cs ⁺ +Sb ⁺³ +2Cl ^- +6H ₂ O → 2Cs _x Sb _y WO ₃ Cl+10HCl+H ₂ (X ≦ 1,y ≦ 1)

Finally, the composite tungsten oxide powder was added into a toluene solvent to prepare a solution with a weight ratio of 20%, and a 6% by weight polymer dispersant was added and ground and dispersed by using 1 mm cerium zirconium beads to obtain a particle diameter of less than 80 nm. The composite tungsten oxychloride grinding dispersion.

The polishing dispersion was mixed with an acrylic resin (product type SSM7, manufactured by Nanya Plastics Co., Ltd.) to form a 20% by weight coating liquid, and the coating liquid was applied to the PET film by wet coating. Drying at 120 ° C for 2 minutes gave a transparent heat-insulating film. The transmittance at a wavelength of 300 to 2000 nm (i.e., VLT% and IR cut%) was measured, and the results are shown in Table 1.

Example 2

The same procedure as in Example 1 was carried out except that cerium chloride and cerium trichloride (SbCl ₃ ) were mixed with water in a ratio of 1 mol to 0.5 mol to prepare a transparent solution B.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Example 3

The transparent solution B was prepared as in Example 2 except that tin trichloride (SnCl ₃ ) was used instead of antimony trichloride (SbCl ₃ ).

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1. The results of the life test trend chart are shown in Fig. 1.

Example 4

The transparent solution B was prepared as in Example 2 except that ruthenium trichloride (BiCl ₃ ) was used instead of ruthenium trichloride (SbCl ₃ ).

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Example 5

The same procedure as in Example 1 was carried out except that cerium chloride and cerium trichloride (SbCl ₃ ) were mixed with water in a ratio of 1 mol to 0.7 mol to prepare a transparent solution B.

The transmittance of the obtained transparent heat-insulating film to a wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1 and Figure 3.

Example 6

Same as in Example 5, but the precipitate was subjected to a filtration treatment to remove the solvent to obtain a wet mud precipitate containing tungsten chloride, cesium chloride and ruthenium trichloride, and the calcination temperature of the high temperature furnace was from room temperature. It rises to 785~815°C (average temperature 800°C).

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Example 7

Same as Example 5, except that the heating rate of the high temperature furnace was changed to 10 ° C per minute.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Example 8

The same procedure as in Example 3 was carried out except that cerium chloride and tin trichloride (SnCl ₃ ) were mixed with water in a ratio of 1 mol to 0.7 mol to prepare a transparent solution B. .

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Example 9

The transparent solution B was prepared in the same manner as in Example 1, except that barium chloride and barium trichloride (SbCl ₃ ) were mixed with water in a ratio of 1 mole to 1.0 mole.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Comparative example 1

Same as Example 5, except that the heating rate of the high temperature furnace was changed to 15 ° C per minute.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Comparative example 2

Same as in Example 1, except that only cesium chloride was mixed with water to prepare a transparent solution B.

The transmittance of the obtained transparent heat-insulating film to a wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1 and Figure 3.

Comparative example 3

The same as in Example 1, except that only cesium chloride was mixed with water to prepare a transparent solution B, and the calcination temperature of the high-temperature furnace was raised from room temperature to 785 to 815 ° C (average temperature of 800 ° C).

The transmittance of the obtained transparent heat-insulating film to a wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1 and Figure 3.

ratio Comparative example 4

In the same manner as in the fifth embodiment, but in the second-stage heat treatment, when the first-stage high-temperature furnace heat treatment is performed, a certain flow of hydrogen (H ₂ ) is introduced, and the high-temperature furnace is heated at a rate of 2 ° C per minute, and the high temperature is applied. The furnace is raised from room temperature to 485 ~ 515 ° C (hereinafter expressed as an average of 500 ° C), and heat treatment is continued for 1 hour; after the temperature is cooled back to room temperature, the second stage of the high temperature furnace heat treatment is performed, and only a certain flow rate is passed. Under high argon conditions, the high temperature furnace was raised from room temperature to 785 ° C to 815 ° C (average temperature 800 ° C) at a rate of 2 ° C per minute, and heat treatment was continued for 1 hour.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Comparative Example 5

The solid tungsten trioxide (WO ₃₎ with a solid cesium carbonate (Cs ₂ CO ₃₎ were uniformly mixed. Next, the mixed powder is placed in a high-temperature furnace, and a certain flow of argon gas and hydrogen gas are introduced, and the high-temperature furnace is raised from room temperature to 485 to 515 ° C under the condition that the heating rate of the high-temperature furnace is 2 ° C per minute ( An average of 500 ° C) and continuous heat treatment for 1 hour.

After the heat treatment is completed, a composite tungsten oxide is obtained, which is identified as a hexagonal crystal halogen-free composite tungsten oxide by an X-ray diffractometer and a scanning electron microscope energy spectrum analyzer.

Finally, the transmittance of the transparent heat-insulating film obtained by the method of Example 1 at a wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Comparative Example 6

Same as Example 5, except that sodium chloride (NaCl) was used in place of cerium chloride to prepare a transparent solution B.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Comparative Example 7

The same procedure as in Example 1 was carried out except that cerium chloride and cerium trichloride (SbCl ₃ ) were mixed with water in a ratio of 1 mol to 1.1 mol to prepare a transparent solution B.

The transmittance of the obtained transparent heat-insulating film for the wavelength of 300 to 2000 nm was measured, and the results are shown in Table 1.

Result :

1. The transparent heat-insulating film prepared in Example 3, after 1000 hours of long-time illumination test, according to the transparent insulation film life test trend chart of FIG. 1, it is apparent that the change of the infrared band blocking rate and the visible light transmittance is kept low. At 10%. Therefore, the transparent heat-insulating film of Example 3 has long-term quality stability and is available for industrial use.

2. For the visible light transmittance and the infrared ray rejection of the wavelength of 300-2000 nm, according to the transparent and heat-insulating total index (VLT%+IR cut%) of Table 1, the transparent heat-insulating films prepared in Examples 1-9 are More than 160, and the transparent heat-insulating films made in Comparative Examples 1-7 as a control group were all less than 150.

It is thus confirmed that the composite tungsten oxychloride of the present invention is suitable for use as a heat insulating material for blocking infrared rays, and is used for forming a transparent heat insulating film, and has excellent barrier properties for an infrared band having a wavelength of 1000 to 2000 nm. The visible light band with a wavelength of 400~600 nm also shows better visible light transmittance.

3. The composite tungsten oxychloride of Example 2-4, containing a chlorine element and using different tin (Sn) or bismuth (Sb) or bismuth (Bi) metal elements co-doped with cerium (Cs) elements, and satisfies co-doping According to the conditions of the heterogeneous ratio Y/X≦1.0, the transparent heat-insulating film produced has a visible light transmittance ranging from 70 to 72 and an infrared blocking ratio ranging from 91 to 92 according to the test results of Table 1.

It is thus confirmed that the composite tungsten oxychloride of the present invention can be co-doped with tin (Sn) or bismuth (Sb) or bismuth (Bi) metal elements and cerium (Cs) elements, and is suitable for making transparent thermal insulation film. .

4. Comparative Example 5 A transparent heat-insulating film was formed using a halogen-free composite tungsten oxide. According to the total transparency and heat insulation index of Table 1, it was apparently far less than the transparent heat-insulating film produced in Examples 1-9.

Therefore, the composition of the composite tungsten oxychloride of the present invention has a preferable infrared band blocking property because it contains chlorine.

5. Analysis and comparison of the transmittance spectrum of FIG. 3, the transparent heat-insulating film obtained in Example 5, and the transparent heat-insulating film produced in Comparative Example 2 and Comparative Example 3 of the control group have excellent visible light band (400) ~600 nm) penetration characteristics and infrared band (1000~2000 nm) barrier properties.

Further, the composite tungsten oxychloride of Example 5 is a chlorine-containing element and is doped with a strontium (Sb) metal element and a cerium (Cs) element. The composite tungsten oxychloride of Comparative Example 2-3 contains a chlorine element and a ruthenium metal element, and is not doped with a bismuth (Sb) metal element.

It is thus confirmed that the composite tungsten oxychloride of the present invention utilizes the result of co-doping of cerium (Cs) element with tin (Sn) or bismuth (Sb) or bismuth (Bi) metal elements, and the resulting transparent heat insulation The film has a multiplication effect, which can significantly improve the infrared band barrier property and the visible light transmittance characteristic of the transparent heat insulating film.

6. The composite tungsten oxychlorides of Examples 1, 2, 5, 9 and Comparative Example 7 were co-doped with a bismuth (Sb) metal element and a cerium (Cs) element, and Examples 1, 2, 5, and 9 The co-doping ratio of 锑(Sb) to 铯(Cs) ranges from 0.1 to 1.0, which satisfies the condition of Y/X≦1.0, but Comparative Example 7 does.

According to the test results in Table 1, under the condition of satisfying Y/X≦1.0, when the ratio of Y/X is larger, the visible light transmittance of the transparent heat-insulating film is relatively reduced, and the infrared group ratio (insulation effect) However, the composite tungsten oxychloride of Comparative Example 7 does not satisfy the condition of Y/X ≦ 1.0, and is not suitable for use as a highly transparent heat-insulating film.

Therefore, the composite tungsten oxychloride method of the present invention can be made into different characteristics by adjusting different Y/X ratios (or co-doping ratios) under the condition of satisfying Y/X≦1.0 according to the needs of different uses. The composite tungsten oxychloride is made into a highly transparent heat-insulating film suitable for different uses.

7. The transparent heat-insulating film obtained in Example 5 and Example 6 has an excellent visible light band penetration with respect to the transparent heat-insulating film produced in Comparative Example 4 according to the total transparency and heat insulation index of Table 1. Transmissive characteristics and infrared band blocking characteristics.

The difference between the three is that in the process of applying high temperature calcination to the composite tungsten oxychloride, the fifth embodiment and the sixth embodiment are subjected to a single sintering heat treatment, and at the same time, hydrogen (H ₂ ) and argon gas are introduced ( Ar), a two-stage heat treatment was applied to Comparative Example 4, and hydrogen gas was supplied during the first-stage heat treatment and argon gas was supplied during the second-stage heat treatment.

It is thus confirmed that the composite tungsten oxychloride method of the present invention only needs to perform a single sintering heat treatment, and simultaneously introduces hydrogen (H ₂ ) and argon (Ar), thereby contributing to the preparation of the composite tungsten oxychloride. The compound has good absorption characteristics in the near-infrared region, and has the characteristics of simple process and cost saving.

8. The transparent heat-insulating film obtained in Example 5 and Example 6 showed that the higher the sintering temperature, the higher the transparency of the obtained composite tungsten oxychloride powder according to the general index of transparency and heat insulation of Table 1.

9. In the same manner, the transparent heat-insulating film obtained in Example 5 and Example 7 was excellent in the transparent heat-insulating film produced in Comparative Example 1 according to the total transparency and heat-insulating index of Table 1. Visible light transmission characteristics and infrared band blocking characteristics.

The difference between the three is that different heating rate conditions are set in the process of applying high temperature sintering to the composite tungsten oxychloride. In Example 5, the temperature increase rate was set to 2 ° C / min, and in Example 7, the temperature increase rate was set to 10 ° C / min, and the temperature increase rate was set to 15 ° C / min with respect to Comparative Example 1.

It is thus confirmed that the composite tungsten oxychloride method of the present invention controls the heating rate of the high temperature furnace to 2 to 10 ° C per minute when performing a single sintering heat treatment, thereby contributing to the composite tungsten oxychloride of the present invention. Good absorption characteristics in the near-infrared region.

1 is a trend chart of life testing of composite tungsten oxychloride particles of the present invention;

2 is a flow chart showing the steps of the method for preparing a composite tungsten oxychloride according to the present invention;

Figure 3 is a graph showing the transmittance of the composite tungsten oxychloride particles of the present invention.

Claims (6)

The invention discloses a method for manufacturing a transparent heat insulating material, which is specially used for manufacturing a transparent heat insulating material having a characteristic of blocking an infrared band of a wavelength of 800 to 2000 nm, and is characterized in that the following steps are included: a. taking tungsten hexachloride dissolved in ethanol to prepare a solution A ; b. taking an appropriate amount of cesium chloride (CsCl) and a tin containing (Sn) or bismuth (Sb) or bismuth (Bi) metal elements together with water to prepare a solution B; c. solution A and solution B is formed by a co-deposition method; d. The precipitate of step c is subjected to a sintering heat treatment at a sintering temperature of 450 to 800 ° C to obtain a composite tungsten oxychloride powder having a chemical formula of Cs _x N _y WO _3-Z Cl _C Wherein Cs is 铯; N is tin (Sn) or bismuth (Sb) or bismuth (Bi); W is tungsten; O is oxygen; X, Y, Z, C are all positive and meet the following conditions: X ≦ 1.0 Y≦1.0; Y/X≦1.0; Z≦0.6 and C≦0.1. A method for producing a transparent heat insulating material according to claim 1, wherein in the step d, the sintering heat treatment is performed in an atmosphere in which hydrogen gas and argon gas are introduced. The method for producing a transparent heat insulating material according to the first or second aspect of the patent application, wherein, in the step d, the temperature is raised from room temperature to a sintering temperature of 450 to 2 °C per minute. 800 ° C, and continued heat treatment for 1-2 hours. The method for preparing a transparent heat insulating material according to claim 1, wherein, under the condition that Y/X≦1.0 is satisfied, different Y/X ratios are adjusted when performing step b, and different blocking infrared bands can be obtained. Characteristic composite tungsten oxychloride powder. A transparent heat insulating material is obtained according to the method of claim 1 of the patent application, and has the infrared band characteristic of blocking wavelength of 800-2000 nm, and the chemical formula is Cs _x N _y WO _3-Z Cl _C , wherein Cs is 铯; N is tin ( Sn) or bismuth (Sb) or bismuth (Bi); W is tungsten; O is oxygen; X, Y, Z, C are positive numbers, and meet the following conditions: X ≦ 1.0; Y ≦ 1.0; Y / X ≦ 1.0 ;Z≦0.6 and C≦0.1. A transparent heat insulating material as described in claim 5, which has an infrared band characteristic of blocking wavelengths of 800 to 1000 nm.